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US6610362B1 - Method of forming a carbon doped oxide layer on a substrate - Google Patents

Method of forming a carbon doped oxide layer on a substrate Download PDF

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Publication number
US6610362B1
US6610362B1 US09/717,517 US71751700A US6610362B1 US 6610362 B1 US6610362 B1 US 6610362B1 US 71751700 A US71751700 A US 71751700A US 6610362 B1 US6610362 B1 US 6610362B1
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Prior art keywords
boron
gas
doped oxide
carbon doped
oxide layer
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Expired - Fee Related
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US09/717,517
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Steven N. Towle
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Intel Corp
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Intel Corp
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Assigned to INTEL CORPORATION, A CORPORATION OF DELAWARE reassignment INTEL CORPORATION, A CORPORATION OF DELAWARE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TOWLE, STEVEN N.
Priority to US10/458,003 priority patent/US6762435B2/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer

Definitions

  • the present invention relates to a method of forming a carbon doped oxide layer on a substrate, e.g., a substrate used to make a semiconductor device.
  • Semiconductor devices include metal layers that are insulated from each other by dielectric layers. As device features shrink, reducing the distance between the metal layers and between metal lines on each layer, capacitance increases. To address this problem, insulating materials that have a relatively low dielectric constant are being used in place of silicon dioxide (and other materials that have a relatively high dielectric constant) to form the dielectric layer that separates the metal lines.
  • a material that may be used to form such a low k dielectric layer is carbon doped oxide (“CDO”). Using this material instead of silicon dioxide to separate metal lines may yield a device having reduced propagation delay, cross-talk noise and power dissipation.
  • CDO carbon doped oxide
  • a conventional process for forming a CDO layer yields a material that has a dielectric constant of about 3.0. In some circumstances, it may be desirable to further reduce the dielectric constant for that layer.
  • FIG. 1 provides a schematic representation of a CVD chamber for a PECVD reactor.
  • a method for forming a carbon doped oxide layer on a substrate comprises introducing into a chemical vapor deposition apparatus sources of carbon, silicon, boron and oxygen, then operating that apparatus under conditions that cause a boron containing carbon doped oxide layer to form on the substrate.
  • a substrate e.g., a silicon wafer upon which various conducting and insulating layers may have been formed
  • a chemical vapor deposition apparatus preferably a PECVD reactor, e.g., PECVD reactor 100 illustrated in FIG. 1 .
  • gases that provide a source of carbon, silicon, boron and oxygen are introduced into the reactor. Those gases may be fed into reactor 100 in the conventional manner.
  • Gases that may provide a source of carbon and silicon include alkyl silane and alkyl oxysilane precursors, for example, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyl phenyl dimethoxysilane, diphenyl dimethoxysilane, and octamethyl cyclotetrasiloxane, as well as others that are well known to those skilled in the art.
  • Gases that provide a source of boron include diborane, borazine, tetraborane, decaborane, methoxydiethylborane, triethylborane, as well as many others.
  • a first gas, which provides the source of silicon and carbon, and a second gas, which provides the source of boron and perhaps also carbon, may be introduced into the PECVD reactor in the same gas stream or different gas streams. Note that while these substances are introduced as gases, they may be liquids at standard temperature and pressure. When an alkyl silane is used as the silicon/carbon source, oxygen or nitrous oxide may be included in the gas stream as a source of oxygen.
  • a ratio of the first gas to the second gas, as fed into the reactor, should be chosen to ensure that the resulting boron containing CDO layer contains between about 3 and about 20 atom % boron and between about 5 and about 50 atom % carbon (both exclusive of hydrogen content), and more preferably includes between about 5 and about 15 atom % boron and between about 20 and about 35 atom % carbon (exclusive of hydrogen content).
  • that layer preferably has a dielectric constant that is less than or equal to about 2.8.
  • helium, argon, or nitrogen into the reactor—in addition to the gases that provide the source of silicon, carbon, boron, and oxygen, as is well understood by those skilled in the art.
  • the presence of carbon in the CDO layer renders that layer hydrophobic even at relatively high levels of boron content.
  • boron doped silicon dioxide glass is highly hydroscopic, greatly reducing its utility as a low-k dielectric material. Process steps that follow deposition of such a boron containing CDO layer (e.g., etching, ashing, and cleaning steps) should be performed in a way that maintains this hydrophobic property.
  • the PECVD reactor may be operated at conventional temperatures, pressures, radio frequency and power. Optimal operating conditions may, of course, depend upon the composition of the gas streams fed into the reactor, the type of reactor used, and the desired properties for the resulting boron containing CDO layer.
  • an annealing step to outgas volatile species, e.g., water, hydrogen and other low molecular weight substances.
  • the temperature chosen for such an annealing step should ensure that the material can withstand the demands that subsequent process steps impose on it. In some applications, applying a temperature of about 400° C. for about 10 minutes should be adequate.
  • the, method of the present invention should reduce the layer's dielectric constant, which may improve semiconductor device performance.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Formation Of Insulating Films (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Abstract

A method of forming a carbon doped oxide layer on a substrate is described. That method comprises introducing into a chemical vapor deposition apparatus a source of carbon, silicon, boron, and oxygen. That apparatus is then operated under conditions that cause a boron containing carbon doped oxide layer to form on the substrate.

Description

FIELD OF THE INVENTION
The present invention relates to a method of forming a carbon doped oxide layer on a substrate, e.g., a substrate used to make a semiconductor device.
BACKGROUND OF THE INVENTION
Semiconductor devices include metal layers that are insulated from each other by dielectric layers. As device features shrink, reducing the distance between the metal layers and between metal lines on each layer, capacitance increases. To address this problem, insulating materials that have a relatively low dielectric constant are being used in place of silicon dioxide (and other materials that have a relatively high dielectric constant) to form the dielectric layer that separates the metal lines.
A material that may be used to form such a low k dielectric layer is carbon doped oxide (“CDO”). Using this material instead of silicon dioxide to separate metal lines may yield a device having reduced propagation delay, cross-talk noise and power dissipation. A conventional process for forming a CDO layer yields a material that has a dielectric constant of about 3.0. In some circumstances, it may be desirable to further reduce the dielectric constant for that layer.
Accordingly, there is a need for an improved process for making a carbon doped oxide insulating layer. There is a need for such a process that generates a CDO material with a reduced dielectric constant, which can be easily integrated into existing processes for making semiconductors. The method of the present invention provides such a process.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 provides a schematic representation of a CVD chamber for a PECVD reactor.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
A method is described for forming a carbon doped oxide layer on a substrate. That method comprises introducing into a chemical vapor deposition apparatus sources of carbon, silicon, boron and oxygen, then operating that apparatus under conditions that cause a boron containing carbon doped oxide layer to form on the substrate. In the following description, a number of details are set forth to provide a thorough understanding of the present invention. It will be apparent to those skilled in the art, however, that the invention may be practiced in many ways other than those expressly described here. The invention is thus not limited by the specific details disclosed below.
In the method of the present invention, a substrate, e.g., a silicon wafer upon which various conducting and insulating layers may have been formed, is placed in a chemical vapor deposition apparatus—preferably a PECVD reactor, e.g., PECVD reactor 100 illustrated in FIG. 1. To form a CDO layer on such a substrate, in accordance with the method of the present invention, gases that provide a source of carbon, silicon, boron and oxygen are introduced into the reactor. Those gases may be fed into reactor 100 in the conventional manner.
Gases that may provide a source of carbon and silicon include alkyl silane and alkyl oxysilane precursors, for example, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyl phenyl dimethoxysilane, diphenyl dimethoxysilane, and octamethyl cyclotetrasiloxane, as well as others that are well known to those skilled in the art. Gases that provide a source of boron include diborane, borazine, tetraborane, decaborane, methoxydiethylborane, triethylborane, as well as many others.
A first gas, which provides the source of silicon and carbon, and a second gas, which provides the source of boron and perhaps also carbon, may be introduced into the PECVD reactor in the same gas stream or different gas streams. Note that while these substances are introduced as gases, they may be liquids at standard temperature and pressure. When an alkyl silane is used as the silicon/carbon source, oxygen or nitrous oxide may be included in the gas stream as a source of oxygen. A ratio of the first gas to the second gas, as fed into the reactor, should be chosen to ensure that the resulting boron containing CDO layer contains between about 3 and about 20 atom % boron and between about 5 and about 50 atom % carbon (both exclusive of hydrogen content), and more preferably includes between about 5 and about 15 atom % boron and between about 20 and about 35 atom % carbon (exclusive of hydrogen content). In addition, that layer preferably has a dielectric constant that is less than or equal to about 2.8.
In some cases, it may be desirable to feed helium, argon, or nitrogen into the reactor—in addition to the gases that provide the source of silicon, carbon, boron, and oxygen, as is well understood by those skilled in the art. The presence of carbon in the CDO layer renders that layer hydrophobic even at relatively high levels of boron content. Without the presence of carbon, boron doped silicon dioxide glass is highly hydroscopic, greatly reducing its utility as a low-k dielectric material. Process steps that follow deposition of such a boron containing CDO layer (e.g., etching, ashing, and cleaning steps) should be performed in a way that maintains this hydrophobic property.
The PECVD reactor may be operated at conventional temperatures, pressures, radio frequency and power. Optimal operating conditions may, of course, depend upon the composition of the gas streams fed into the reactor, the type of reactor used, and the desired properties for the resulting boron containing CDO layer. After the CDO layer is deposited, it may be desirable to apply an annealing step to outgas volatile species, e.g., water, hydrogen and other low molecular weight substances. The temperature chosen for such an annealing step should ensure that the material can withstand the demands that subsequent process steps impose on it. In some applications, applying a temperature of about 400° C. for about 10 minutes should be adequate.
By adding boron to a PECVD deposited CDO layer, the, method of the present invention should reduce the layer's dielectric constant, which may improve semiconductor device performance. Although the foregoing description has specified certain steps, materials, and equipment that may be used in such a method, those skilled in the art will appreciate that many modifications and substitutions may be made. Accordingly, it is intended that all such modifications, alterations, substitutions and additions be considered to fall within the spirit and scope of the invention as defined by the appended claims.

Claims (8)

What is claimed is:
1. A method of forming a carbon doped oxide layer on a substrate comprising:
introducing into a chemical vapor deposition apparatus a first gas that comprises an alkyl oxysilane and a second gas that comprises a source of boron; then
operating the apparatus under conditions that cause a boron containing carbon doped oxide layer to form on the substrate,
wherein the ratio of the first gas to the second gas, as introduced into the chemical vapor deposition apparatus, ensures that the resulting boron containing carbon doped oxide layer contains between about 5 and about 15 atom % boron and between about 20 and about 35 atom % carbon, exclusive of hydrogen content.
2. The method of claim 1 wherein the chemical vapor deposition apparatus is a plasma enhanced chemical vapor deposition reactor.
3. The method of claim 2 wherein the resulting boron containing carbon doped oxide has a dielectric constant that is less than or equal to about 2.8.
4. The method of claim 3 wherein the alkyl oxysilane is selected from the group consisting of methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyl phenyl dimethoxysilane, and diphenyl dimethoxysilane.
5. The method of claim 4 wherein the source of boron is a gas that is selected from the group consisting of diborane, borazine, tetraborane, decaborane, methoxydiethylborane, and triethylborane.
6. A method of forming a semiconductor device comprising: forming on a substrate a boron containing carbon doped oxide layer by
introducing into a plasma enhanced chemical vapor deposition reactor a first gas that comprises an alkyl oxysilane and a second gas that comprises a source of boron; then
operating the reactor under conditions that cause a boron containing carbon doped oxide layer to form on the substrate,
wherein the ratio of the first gas to the second gas, as introduced into the reactor, ensures that the resulting boron containing carbon doped oxide layer contains between about 5 and about 15 atom % boron and between about 20 and about 35 atom % carbon, exclusive of hydrogen content
7. The method of claim 6 wherein the source of boron is a gas that is selected from the group consisting of diborane, borazine, tetraborane, decaborane, methoxydiethylborane, and triethylborane.
8. The method of claim 7 wherein the resulting boron containing carbon doped oxide has a dielectric constant that is less than or equal to about 2.8.
US09/717,517 2000-11-20 2000-11-20 Method of forming a carbon doped oxide layer on a substrate Expired - Fee Related US6610362B1 (en)

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